Miticides comprising an ester of 4 6-dinitro-2-sec. butyl-phenol and 2 4 5 4&#39;-tetrachlorodiphenyl sulfide or sulfone

ABSTRACT

PESTICIDAL COMPOSITIONS COMPRISING 4,6-DINITRO-2-SEC. BUTYLPHENYL DIMETHYL ACRYLATE (BINAPACRYL), 4,6-DINITRO2-SEC. BUTYLPHENYL STEARATE OF 4,6-DINITRO-2-SEC. BUTYLPHENYL ISOPROPYL CARBONATE (DINOBUTON) IN COMBINATION WITH 2,4,5,4&#39;&#39;-TETRACHLORODIPHENYL SULFIDE (TETRASUL) OR 2,4,5,4&#39;&#39;TETRACHLORODIPHENYL SULFONE (TETRADIFON). THE COMBINATIONS HAVE A SYNERGISTIC EFFECT AND ARE ESPECIALLY USEFUL IN THE CONTROL OF SPIDER MITES.

US. Cl. 424-301 3 Claims ABSTRACT OF THE DISCLOSURE Pesticidal compositions comprising 4,6-dinitro-2-sec. butylphenyl dimethyl acrylate (binapacryl), 4,6-dinitro- 2-sec. butylphenyl stearate or 4,6 dinitro-2-sec. butylphenyl isopropyl carbonate (dinobuton) in combination with 2,4,5,4'-tetrachlorodiphenyl sulfide (tetrasul) or 2,4,5,4'- tetrachlorodiphenyl sulfone (tetradifon). The combinations have a synergistic effect and are especially useful in the control of spider mites.

The present invention relates to pesticides useful for controlling spider mites (tetranychidae).

It is known to use 4,6-dinitro-2-sec. butyl-phenyl esters (DNBP esters) to combat spider mites, for example DNBP dimethylacrylate (binapacryl), DNBP stearate, or DNBP isopropyl carbonate (dinobuton),

It is not possible, however, satisfactorily to control all strains of spider mites with the aforesaid DNBP esters.

It is also known to use 2,4,5,4'-tetrachloro-diphenyl sulfide (tetrasul) and 2,4,5,4'-tetrachlorodiphenyl-sulfone (tetradifon) as acaricidal agents. These latter compounds only destroy the eggs and nymphs of the mites and not their adult forms.

The present invention provides agents for combating spider mites characterized by a content of a synergistic combination of DNBP dimethylacrylate (binapacryl), or DNBP stearate, or DNBP isopropyl carbonate (dinobuton) with 2,4,5,4'-tetrachlorodiphenyl sulfide (tetrasul) or 2, 4,5,4-tetrachlorodiphenyl sulfone (tetradifon). A ratio of the active ingredients of about 3 to 7 parts by weight of the DNBP ester to about 1 part by weight of tetrasul or tetradifon is preferred.

Should none of the aforesaid single active ingredients show a sufiicient effect, the pests can be destroyed by a combination of the active ingredients according to the invention. As compared with the effects of the individual components, the combinations of the active ingredients have a synergistic effect, especially on spider mites. The effect is illustrated in the following Example 3. Moreover, the combinations according to the invention have a good effect on mildew (Erysiphaceen).

The pesticides according to the invention are advantageously used in the form of an emulsifiable concentrate containing 10 to 70% by weight of the mixture of effective ingredients and 5 to by weight of a wetting agent, the remainder to 100% by weight being an organic solvent.

The pesticides of the invention can also be used in the form of a Wettable powder or of a paste containing 10 to 80% by weight of the mixture of active ingredients and 3 to 10% by Weight of a wetting agent and/0r dispersing agent, the remainder to 100% by weight being one or several solid inert substances.

Suitable wetting agents are, for example, ethoxylated alkyl phenols, ethoxylated oleyl or stearyl amines and United States Patent O 3,646,212 Patented Feb. 29, 1972 alkyl or alkyl-aryl sulfonates. Suitable dispersing agents are, for example, sodium lignin sulfonate, sodium 2,2- dinaphthylmethane 6,6 disulfonate, sodium dibutylnaphthalene-sulfonate or sodium oleylmethyltaurine.

Suitable organic solvents are inert liquids such as butanol, cyclohexanone, dimethyl formamide, toluene, xylene or higher boiling aromatic hydrocarbons as well as ketones, for example methylethyl ketone, mehylisobutyl ketone or isophorone.

As inert substances there may be used mineral substances such as aluminum silicates, argillaceous earths, kaolin, kieselguhr or hydrated silicic acids.

Suitable grinding auxiliaries are inorganic or organic salts such as sodium sulfate, ammonium sulfate, sodium carbonate, sodium bicarbonate, sodium thiosulfate, sodium stearate or sodium acetate.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight unless otherwise stated.

EXAMPLE 1 Wettable powders having a content of active ingredients of 4 parts of DNBP ester and 1 part of tetrasul or tetradifon were obtained by mixing:

40 parts of 4,6-dinitro-2-sec. butylphenyl dimethylacrylate (binapacryl), or 4,6-dinitro-2-sec. butylphenyl stearate, or 4,6-dinitro-2-sec. butylphenyl isopropyl carbonate (dinobuton),

10 parts of 2,4,5,4'-tctrachlorodiphenyl sulfide (tetrasul),

or 2,4,5,4-tetrachlorodiphenyl sulfone (tetradifon),

39 parts of kieselguhr,

2 parts of polyvinyl acetate (degree of polymerization 70 saponification number 88),

7 parts of sodium alkylnaphthalene sulfonate,

2 parts of sodium dimethylnaphthalene sulfonate.

EXAMPLE 2 Emulsifiable concentrates having a content of active ingredients of 3 parts of the DNBP esters specified in Example 1 and 1 part of tetrasul or tetradifon are obtained by mixing:

30 parts of DNBP ester (as specified in Example 1),

10 parts of tetrasul or tetradifon,

54 parts of xylene,

6 parts of an emulsifier mixture consisting of sodium alkylphenyl sulfonate and ethoxylated tributylphenol.

EXAMPLE 3 Small apple trees in pots were infested with fruit tree red spiders (Metatetranyclzus ulmi) of the strain Dardar. The trees were kept in the greenhouse until a complete population had grown on the leaves, i.e. a great number of eggs, larvae, nymphs and imagoes. A few of the trees were sprayed With aqueous spray liquors of the combinations according to the invention in the form of emulsions made with the emulsifiable concentrates specified in Example 2. The combinations contained the active ingredients in a ratio of 3:1.

In the manner described in Example 2 further combinations were prepared containing 35 parts of one of the indicated DNBP esters and 5 parts of tetrasul or tetradifon. In these combinations the active ingredients were contained in a ratio of 7:1. Further apple trees were treated with aqueous spray liquors made from the corresponding emulsifiable concentrates.

Other apple trees were treated with spray liquors containing as active ingredient solely binapacryl, DNBP stearate, dinobuton, tetrasul, or tetradifon, respectively.

After the treatment with the respective spray liquor all apple trees were kept in the greenhouse at an average temperature of 20 C. in an atmosphere having a relative moisture content of 45%. 10 days after spraying the trees were examined with the microscope to determine the elfectiveness of the spray liquors. The degree of eflectiveness indicated in the following tables is given in percent of killed pests according to the method of W. S. Abbott A Method of Computing the Effectiveness of an Insecticide Journal of Economic Entomology, volume 18, pages 265-267 (1935).

The following Tables I-III show that the known active ingredients had no satisfactory etfect when used alone. As compared therewith, the combinations of active ingredients according to the invention had a surprising synergistic effect.

TABLE I Percent eflcctiveness with total population of metatetranychus ulmi 10 days after treatment (average of 3 tests) Percent active ingredient in spray liquor Tetrasul Tetradifon Bin apacryl Untreated control 3 TABLE II Percent ofiectivenoss with total population of metatetranychus ulmi 10 days after treatment (average Tctradifon i 3 tests) Percent active ingredientin spray liquor DNBP-stearate Tetrasul Untreated control g 3 TABLE III Percent efi ect-ivcness with total popula tion of metatetrauychus uhui 10 days after treatment (average of 3 tests) lclccnt active ingredient in spray liquor Tetrasul Tctraditon Dinobuton Untreated control 4 What is claimed is:

1. A miticidal composition comprising as the effective ingredient thereof a mixture of from about 3 to 7 parts by Weight of an ester of 4,6-dinitro-2-sec. butylphenol selected from the group consisting of the dimethylacrylate, stearate, and isopropyl carbonate With 1 part by Weight of a member selected from the group consisting of 2,4,5,4'- tetrachlorodiphenyl sulfide and 2,4,5,4'-tetrachlorodiphenyl sulfone.

2. The miticidal composition of claim 1 in the form of an emulsifiable concentrate comprising 10 to percent of said effective ingredient and 5 to 15 percent of a wetting agent, by weight of said composition, in an organic solvent.

3. The miticidal composition of claim 1 in the form of a Wettable powder comprising 10 to percent of said efiective ingredient and 3 to 10 percent of at least one member selected from the group consisting of wetting agents and dispersing agents, by weight of said composition, in admixture with an inert solid.

References Cited UNITED STATES PATENTS 3,054,719 9/1962 Uhlenbroek et a1. 42 4337 3,123,522 3/1964 Scherer et al. 424301 X 3,234,260 2/1966 Pianka et al 424301 X OTHER REFERENCES Merck Index, 8th ed. (1968), pp. 1024-5.

ALBERT T. MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner US. Cl. X.R. 

